CA3200243A1 - Dispersant for lithium ion battery and preparation method thereof, positive slurry, and lithium ion battery - Google Patents
Dispersant for lithium ion battery and preparation method thereof, positive slurry, and lithium ion batteryInfo
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- CA3200243A1 CA3200243A1 CA3200243A CA3200243A CA3200243A1 CA 3200243 A1 CA3200243 A1 CA 3200243A1 CA 3200243 A CA3200243 A CA 3200243A CA 3200243 A CA3200243 A CA 3200243A CA 3200243 A1 CA3200243 A1 CA 3200243A1
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- dispersant
- monomer
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- lithium ion
- ion battery
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/06—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
- C08F226/10—N-Vinyl-pyrrolidone
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L39/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Compositions of derivatives of such polymers
- C08L39/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C08L39/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
- C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
- C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
Description
[0001] The present disclosure claims priority to Chinese Patent Application No.
6 202011361699.6, entitled "DISPERSANT FOR LITHIUM ION BATTERY AND
7 PREPARATION METHOD THEREOF, POSITIVE SLURRY, POSITIVE PLATE, AND
LITHIUM ION BATTERY" and filed on November 28, 2020. The entire content of the above-9 referenced application is incorporated herein by reference.
12 [0002]
The present disclosure relates to the technical field of lithium ion batteries, and more specifically, to a dispersant for a lithium ion battery and a preparation method thereof, a 14 positive slurry, and a lithium ion battery.
17 [0003]
Components of a positive slurry of a lithium ion battery mainly includes a positive active material, a conductive agent, a binder, and a solvent. In response to increasing requirements for battery performance, increasing requirements are imposed on a manufacturing process of a positive slurry of a battery. On the one hand, a dispersion effect of a positive active material and a conductive agent in the positive slurry needs to be improved to improve the uniformity of a positive plate. On the other hand, a solid content of the positive slurry needs to be CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 increased to improve the coating performance of the positive slurry and improve the yield and 2 productivity of the positive plate. Adding dispersant additives to the positive slurry becomes a 3 mainstream method in the industry to improve the dispersion effect of the positive slurry.
4 [0004] Few types of dispersants are applicable to existing lithium ion batteries, mainly including polyvinyl pyrrolidone (PVP) and polyacrylamide (PAM). However, these dispersants 6 have a limited dispersion capability for the positive slurry, and are usually added at a large amount, 7 which, however, correspondingly reduces a mass ratio of the positive active material in the positive 8 material layer formed by the positive slurry, thus reducing a specific capacity of a battery.
9 Therefore, dispersants having an excellent dispersion capability for the positive slurry need to be developed to achieve a desirable slurry dispersion effect with a small dosage of dispersant.
13 [0005] In view of the above, embodiments of the present disclosure provide a dispersant 14 for a lithium ion battery and a preparation method thereof, a positive slurry, and a lithium ion battery. The dispersant for a lithium ion battery may have functions of both a binder and a 16 dispersant, and can reduce an amount of binder used in an existing positive slurry, which can satisfy 17 a requirement for a high dispersion of the positive slurry while avoiding a reduction of a specific 18 capacity of a battery caused by a reduction of a content of a positive active material.
19 [0006] In a first aspect, the present disclosure provides a dispersant for a lithium ion battery. The dispersant includes a structural unit A derived from a solvophilic monomer, a 21 structural unit B derived from a conjugated diene monomer, and a structural unit C derived from CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 a high-adhesion monomer. The solvophilic monomer includes one or both of N-vinylpyrrolidone 2 and an acrylamide monomer, the high-adhesion monomer includes one or both of an unsaturated 3 nitrile monomer and an acrylate monomer.
4 [0007] The structural unit B derived from the conjugated diene monomer is configured to provide a molecular skeleton function for the dispersant, and enables a molecular chain of the 6 dispersant to have a certain flexibility, so that the dispersant has a low electrolyte swelling property.
7 The solvophilic monomer is configured to provide the dispersant with the structural unitA that has 8 strong affinity with a solvent of a positive slurry (such as N-methylpyrrolidone (NM P) or N, N-9 dimethylformamide (DM F)), to increase the solubility of the dispersant with the solvent of the positive slurry. The high-adhesion monomer is configured to enable the dispersant to have the 11 structural unit C of nitrile and/or ester polar groups, so that the dispersant generates a strong 12 intermolecular interaction to dispersed particles (positive active material particles, conductive 13 agent particles, and the like), and therefore can be easily adsorbed on surfaces of the dispersed 14 particles and an interface of the solvent, thereby enabling the positive material, the conductive agent, and the like to achieve excellent dispersion effects in the positive slurry of the lithium ion 16 battery, and preventing the dispersed particles from reuniting again. In addition, a dispersion time 17 is short, and a low dispersant dosage is required. In addition, during drying of the positive slurry, 18 the dispersant may be used to bond the dispersed particles or bond the dispersed particles and the 19 current collector, to provide a function of a binder, thereby avoiding a reduction of the mass ratio of the positive active material in the positive slurry.
21 [0008] Therefore, the dispersant has the dispersion and bonding functions, which can CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 ensure excellent dispersion effects of the positive active material and the conductive agent in the 2 positive slurry of the lithium ion battery. Moreover, the dispersant can partially or completely 3 replace the binder in the positive slurry, so that the content of the positive active substances in the 4 positive plate prepared from the positive slurry can substantially remain unchanged, thereby avoiding a reduction of the energy density of the battery due to the addition of the dispersant.
6 [0009] In some implementations of the present disclosure, the dispersant includes a 7 copolymer including the structural unit A, the structural unit B, and the structural unit C. The 8 copolymer may include any one or more of a random structure, a block structure, an alternating 9 structure, and a graft copolymerization structure.
[0010] In some implementations of the present disclosure, based on a total amount of 11 the dispersant, a molar proportion of the structural unit A is in a range of 5%-50%, a molar 12 proportion of the structural unit B is in a range of 30%-90%, and a molar proportion of the 13 structural unit C is in a range of 1%-30%. In this way, the dispersant can have a certain affinity to 14 solvents, a certain affinity to to-be-dispersed particles, and a certain flexibility, thereby achieving a desirable dispersion effect.
16 [0011] In some implementations of the present disclosure, the acrylamide monomer 17 includes one or more of acrylamide, methylacrylamide, N, N-dimethylacrylamide, N-18 hydroxymethylacrylamide, N-butoxymethylacrylamide, N-hydroxymethylmethylacrylamide, and 19 N-butoxymethylmethylacrylam ide.
[0012] In some other implementations of the present disclosure, the solvophilic 21 monomer is N-vinylpyrrolidone. Compared with the acrylamide monomer, the N-vinylpyrrolidone CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 has higher structural stability and higher affinity to the most common solvent in the positive slurry, 2 that is, NMP.
3 [0013]
In some implementation of the present disclosure, a carbon atom number of the conjugated diene monomer is not less than 4, such as 4-12. Exemplarily, the conjugated diene monomer may include one or more of 1,3-butadiene, isoprene, 2,3-dimethy1-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-decadiene, and 2-methyl-1,5-heptadiene.
7 [0014]
In some implementation of the present disclosure, the unsaturated nitrile monomer includes one or more of acrylonitrile, a-methacrylonitrile, a-ethylacrylonitrile, butenenitrile (such as 3-butenenitrile or 2-butenenitrile), 2-methyl-2-butenenitrile, 2-methyl-3-butenenitri le, 4-methyl-3-pentanenitri le, a-chloroacrylonitrile, a-bromoacrylonitrile, 2-11 ethoxyacrylonitrile, and 3,3-dimethoxy-2-acrylonitrile.
12 [0015]
In some implementation of the present disclosure, the acrylate monomer includes one or more of alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, and hydroxyalkyl methacrylate. Exemplary acrylate monomers may include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, tert butyl acrylate, tert butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dodecyl acrylate, dodecyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl 18 methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl acrylate, 19 glycidyl methacrylate, but are not limited thereto.
[0016] In some implementations of the present disclosure, the high-adhesion monomer is the unsaturated nitrile monomer. Compared with the acrylate monomer, the unsaturated nitrile
3 [0017] In some implementations of the present disclosure, the dispersant is polymerized 4 from a monomer raw material including the solvophilic monomer, the conjugated diene monomer, and the high-adhesion monomer described above. In some other implementations of the present
[0018] In some implementation of the present disclosure, a weight average molecular 11 weight of the dispersant is in a range of 100000-600000. The dispersant with the weight average 12 molecular weight in the range can have desirable mechanical properties such as stiffness and 13 desirable flexibility, thereby facilitating subsequent processing and utilization. For example, the 14 weight average molecular weight of the dispersant may be 150000, 200000, 300000, 350000, 400000, 450000, 500000, 550000, or 600000.
16 [0019] The dispersant provided in the first aspect of the present disclosure has the 17 dispersion and bonding functions, and can achieve a desirable dispersion effect of the positive 18 active material and the conductive agent in the positive slurry of the lithium ion battery within a 19 short time, and enables the positive slurry to have a high solid content, which can improve the preparation efficiency and the product yield of the positive plate. In addition, the dispersant 21 partially or completely replaces the existing binder in the positive slurry, so that a mass ratio of the CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 positive active material in the positive plate is not reduced, thereby ensuring a battery capacity.
2 Moreover, the dispersant can improve the flexibility of the positive plate.
3 [0020] In a second aspect, the present disclosure provides a method for preparing a 4 dispersant for a lithium ion battery, including:
performing a polymerization reaction on a monomer raw material including a solvophilic 6 monomer, a conjugated diene monomer, and a high-adhesion monomer. The solvophilic monomer 7 includes one or both of N-vinylpyrrolidone and an acrylamide monomer. The high-adhesion 8 monomer includes one or both of an unsaturated nitrile monomer and an acrylate monomer.
9 [0021] In some implementations of the present disclosure, the preparation method further includes: performing a hydrogenation reaction on a ploymer formed through the 11 polymerization reaction of the monomer raw material. In other words, in this case, the method for 12 preparing a dispersant includes: performing the polymerization reaction on the monomer raw 13 material to obtain a dispersant precursor, and performing a hydrogenation reaction on the 14 dispersant precursor. The hydrogenation reaction can reduce some or all double bonds in the dispersant precursor obtained through the polymerization reaction of the monomer raw material, 16 thereby enhancing the antioxidant ability of the dispersant at a high voltage.
17 [0022] In some implementations of the present disclosure, the hydrogenation reaction 18 may be performed by using precious metal such as Pt as a catalyst and hydrogen as a reducing 19 agent.
[0023] In some implementations of the present disclosure, based on a total mass of the 21 monomer raw material, a proportion of the solvophilic monomer is in a range of 5%-50%, a CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 proportion of the conjugated diene monomer is in a range of 40%-90%, and a proportion of high-2 adhesion monomer is in a range of 1%-20%. In some other implementations of the present 3 disclosure, based on a total mass of the monomer raw material, a proportion of the solvophilic 4 monomer is in a range of 5%-30%, a proportion of the conjugated diene monomer is in a range of 50%-80%, and a proportion of high-adhesion monomer is in a range of 5%-20%.
6 [0024] The above polymerization reaction is not special specially defined, which may 7 be, for example, solution polymerization, mulsion polymerization, suspension polymerization, or 8 bulk polymerization. In some implementations of the present disclosure, the above polymerization 9 reaction is the solution polymerization. The solution polymerization includes: dissolving the monomer raw material and an initiator in a solvent, performing polymerization at a specific 11 temperature, and performing solid-liquid separation and drying on a resulting reaction liquid.
12 [0025] The initiator may be a thermal initiator and/or a photoinitiator. For example, the 13 initiator is the thermal initiator. The thermal initiator may be one or more of aqueous initiators such 14 as potassium persulfate, sodium persulfate, and ammonium persulfate, or may be one or more of oily initiators such as azobisisobutyronitrile, azobisisoheptonitrile, and benzoyl peroxide. In this 16 case, a temperature of the polymerization reaction may be in a range 40 C-80 C, and a time of the 17 polymerization reaction may be in a range 2h-24h. The aqueous initiators or the oily initiators may 18 be selected according to the monomer raw material and the solvent that is used.
19 [0026] In some implementations of the present disclosure, in the solution polymerization process, a chain transfer agent may be further added to the solvent to control a 21 molecular chain length of the resulting polymer. Exemplary chain transfer agents may include CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 ethyl acetate, butyl acetate, acetone, diethyl carbonate, methyl tertiary butyl ether, isopropanol, 2 ethanol, methanol, dodecyl mercaptan, and the like.
3 [0027]
The method for preparing a dispersant provided in the second aspect of the present disclosure is simple and easy in operation, requires low energy consumption, and has a controllable reaction degree, which is applicable to industrialized production.
6 [0028]
A third aspect of the present disclosure further provides a positive slurry.
The positive slurry includes a positive active material, a conductive agent, a dispersant, and a solvent.
The dispersant is the dispersant described in the first aspect of the present disclosure or a dispersant prepared by using the preparation method described in the second aspect of the present disclosure.
[0029] Since the dispersant has the dispersion and bonding functions, the positive slurry may not include the conventional binder in the field of batteries. In this case, it may be understood that the above dispersant completely replaces the binder. In some implementations of the present 13 disclosure, a mass fraction of the dispersant in the positive slurry does not exceed 5%.
14 [0030]
Certainly, in other implementations of the present disclosure, the positive slurry may include a binder. In order to avoid reducing a mass fraction of the positive active material in the positive material layer, a sum of the mass fractions of the dispersant and the binder in the 17 positive slurry does not exceed 5%.
[0031] The above positive active material, binder, and conductive agent are conventional choices in the field of batteries. The binder may be selected from one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), polyvinyl alcohol (PVA), styrene butadiene rubber (SBR), polyacrylonitrile (PAN), polyimide (PI), polyacrylic acid (PAA), CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 polyacrylate, polyolefin, sodium carboxymethyl cellulose (CMC), and sodium alginate. The 2 positive active material may be at least one of lithium iron phosphate, lithium manganese 3 phosphate, lithium manganese iron phosphate, lithium vanadium phosphate, lithium cobalt 4 phosphate, lithium cobalt oxide (LiCo02), lithium manganese oxide, lithium nickel oxide, lithium nickel cobalt oxide, lithium nickel manganese oxide, nickel cobalt manganese (NCM) ternary 6 material, and nickel cobalt aluminum (NCA) ternary material. The conductive agent may include 7 at least one of a carbon nanotube, carbon black, and graphene, but is not limited thereto. A surface 8 of the conductive agent may have functional groups such as carboxylic groups or hydroxyl groups, 9 to facilitate dispersion in the positive slurry. The dispersant has desirable affinity to both positive active material particles and conductive agent particles.
11 [0032] The positive slurry provided in the third aspect of the present disclosure has a 12 high solid content, especially a high content of the positive active material, and has desirable 13 dispersibility, is unlikely to settle, and may be stored for a long time.
14 [0033] A fourth aspect of the present disclosure further provides a lithium ion battery.
The lithium ion battery includes a positive plate. The positive plate includes a current collector and 16 a positive material layer arranged on the current collector. The positive material layer includes a 17 positive active material, a conductive agent, a binder, and a dispersant. The dispersant is the 18 dispersant described in the first aspect of the present disclosure or a dispersant prepared by using 19 the preparation method described in the second aspect of the present disclosure. The lithium ion battery further includes a negative plate and a membrane and an electrolyte located between the 21 positive plate and the negative plate. It should be noted that the negative plate, the membrane, and CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 the electrolyte are all conventional structures of a battery and therefore are not described in detail 2 herein.
3 [0034] Further, the positive material layer in the lithium ion battery may be formed by 4 coating and drying the positive slurry described in the third aspect of the present disclosure. The positive slurry has a high solid content and a low solvent content, and can be dried in a short time 6 to obtain the positive plate, which improves the preparation efficiency of the positive plate. Since 7 the drying time is short, the positive plate is unlikely to crack, and the yield is high. In addition, 8 the positive plate further has desirable flexibility and can be easily assembled into a battery.
DETAILED DESCRIPTION
11 [0035] The following provides exemplary implementations of the present disclosure. It 12 should be noted that a person of ordinary skill in the art may make several improvements and 13 refinements without departing from the principles of the present disclosure. These improvements 14 and refinements are considered to fall within the protection scope of the present disclosure.
[0036] The present disclosure is further described below through the following 16 embodiments.
17 [0037] Embodiment 1 18 [0038] A method for preparing a dispersant for a lithium ion battery includes:
19 dissolving N-vinylpyrrolidone, 1,3-butadiene, and acrylonitrile in N, N-dimethylformamide (DM F) at a mass ratio of 40:40:20, adding an initiator azobisisobutyronitrile 21 and a chain transfer agent dodecyl nnercaptan, performing polymerization at 60 C for 4 hours at a CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 pressure of 4 MPa, performing cooling to terminate the reaction, washing and drying a resulting 2 reactant to obtain a dispersant 1', and hydrogenating the dispersant l' to obtain a dispersant 1. A
3 weight average molecular weight of the dispersant 1 is measured as 500000.
4 [0039] A method for preparing a positive plate includes:
dissolving 1.5 g of binder PVDF in 40 g of N-methylpyrrolidone (NM P), and adding 0.5 g of the above dispersant 1 after 6 full dissolution, and performing stirring for 20 min; adding 20 g of carbon nanotube dispersion 7 (solvent: NMP, solid content: 5 wt%) and performing stirring for 20 min;
adding 97 g of lithium 8 iron phosphate positive active material and performing stirring for 1.5 h to obtain a positive slurry;
9 and coating the positive slurry on aluminum foil and performing drying at 130 C for 30 min to form a positive material layer, thereby completing the production of a lithium iron phosphate 11 positive plate.
12 [0040] Embodiment 2 13 [0041] A method for preparing a dispersant for a lithium ion battery includes:
14 dissolving N-vinylpyrrolidone, 1,3-diene, and 2-methyl-2-butenenitrile in DMF at a mass ratio of 5:80:15, adding an initiator azobisisobutyronitrile and a chain transfer agent dodecyl 16 mercaptan, performing polymerization at 60 C for 4 hours at a pressure of 4 M Pa, performing 17 cooling to terminate the reaction, washing and drying a resulting reactant to obtain a dispersant 2', 18 and hydrogenating the dispersant 2' to obtain a dispersant 2. A weight average molecular weight 19 of the dispersant 2 is measured as 600000.
[0042] In a method for preparing a positive plate, 0.5 g of dispersant 1 in Embodiment 21 1 is replaced with 1.5 g of dispersant 2, 1.5 g of binder PVDF is replaced with 0.5 g of PVDF, and CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 other conditions are the same as those in Embodiment 1.
2 [0043] Embodiment 3 3 [0044] A method for preparing a dispersant for a lithium ion battery includes:
4 dissolving N-vinylpyrrolidone, 1,3-butadiene, and butyl acrylate in DM F in a mass ratio of 30:65:5, adding an initiator azobisisobutyronitrile and a chain transfer agent isobutanol, 6 performing polymerization at 60 C for 4 hours at a pressure of 4 MPa, performing cooling to 7 terminate the reaction, and washing and drying a resulting reactant to obtain a dispersant 3. A
8 weight average molecular weight of the dispersant 3 is measured as 150000.
9 [0045] In a method for preparing a positive plate, 0.5 g of dispersant 1 in Embodiment 1 is replaced with 1 g of dispersant 3, 1.5 g of binder PVDF is replaced with 1 g of PVDF, and 11 other conditions are the same as those in Embodiment 1.
12 [0046] Embodiment 4 13 [0047] A method for preparing a dispersant for a lithium ion battery includes:
14 dissolving N-vinylpyrrolidone, 1,3-butadiene, and butyl acrylate in DM F in a mass ratio of 40:40:20, adding an initiator azobisisobutyronitrile and a chain transfer agent isobutanol, 16 performing polymerization at 60 C for 4 hours at a pressure of 4 MPa, performing cooling to 17 terminate the reaction, washing and drying a resulting reactant to obtain a dispersant 4', and 18 hydrogenating the dispersant 4' to obtain a dispersant 4.A weight average molecular weight of the 19 dispersant 4 is measured as 550000.
[0048] In a method for preparing a positive plate, 0.5 g of dispersant 1 in Embodiment 21 1 is replaced with 1.5 g of dispersant 4, 1.5 g of binder PVDF is replaced with 0.5 g of PVDF, and CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 other conditions are the same as those in Embodiment 1.
2 [0049] Embodiment 5 3 [0050] A method for preparing a dispersant for a lithium ion battery includes:
4 dissolving acrylamide, isoprene, and a-ethylacrylonitrile in DM F at a mass ratio of
[0051] A method for preparing a positive plate includes: dissolving 0.8 g of binder
NMP, solid content: 5
17 ternary positive plate.
18 [0052] Embodiment 6 19 [0053] A method for preparing a dispersant for a lithium ion battery includes:
dissolving N-vinylpyrrolidone, 1,3-hexadiene, and acrylonitrile in dioxane at a mass ratio 21 of 15:80:5, adding an initiator azobisisobutyronitrile and a chain transfer agent dodecyl mercaptan, CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 performing polymerization at 60 C for 4 hours at a pressure of 4 MPa, performing cooling to 2 terminate the reaction, washing and drying a resulting reactant to obtain a dispersant 6', and 3 hydrogenating the dispersant 6' to obtain a dispersant 6.A weight average molecular weight of the 4 dispersant 6 is measured as 300000.
[0054] In a method for preparing a positive plate, 0.4 g of dispersant 5 in Embodiment 6 5 is replaced with 0.6 g of dispersant 6, 0.8 g of binder PVDF is replaced with 0.6 g of PVDF, and 7 other conditions are the same as those in Embodiment 5.
8 [0055] Embodiment 7 9 [0056] A method for preparing a dispersant for a lithium ion battery includes:
dissolving N-hydroxymethylacrylamide, 1,3-butadiene, and acrylonitrile in DM F
at a mass 11 ratio of 10:75:15, adding an initiator azobisisobutyronitrile and a chain transfer agent ethyl acetate, 12 performing polymerization at 60 C for 4 hours at a pressure of 4 MPa, performing cooling to 13 terminate the reaction, washing and drying a resulting reactant to obtain a dispersant 7', and 14 hydrogenating the dispersant 7' to obtain a dispersant 7.A weight average molecular weight of the dispersant 7 is measured as 600000.
16 [0057] In a method for preparing a positive plate, 0.4 g of dispersant 5 in Embodiment 17 5 is replaced with 0.8 g of dispersant 7, 0.8 g of binder PVDF is replaced with 0.4 g of PVDF, and 18 other conditions are the same as those in Embodiment 5.
19 [0058] The following comparative examples 1-2 are set up below to highlight the beneficial effects of the present disclosure.
21 [0059] Comparative example 1 CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 [0060] A main difference between a positive plate in Comparative example 1 and that 2 in Embodiment 1 is that no dispersant is added, 2 g of PVDF is used, and a larger amount of solvent 3 is used during the preparation of the lithium iron phosphate positive plate.
4 [0061] A method for preparing a lithium iron phosphate positive plate in Comparative example 1 includes: fully dissolving 2 g of binder PVDF in 50 g of NMP; adding 20 g of carbon 6 nanotube NMP dispersion (solid content: 5 wt%), and performing stirring for 20 min; adding 97 g 7 of lithium iron phosphate positive active material and performing stirring for 3 h to obtain a 8 positive slurry; and coating the positive slurry on aluminum foil and performing drying at 130 C
9 for 30 min to form a positive material layer, thereby completing the production of a lithium iron phosphate positive plate.
11 [0062] Comparative example 2 12 [0063] A main difference between a ternary positive plate in Comparative example 2 13 and that in Embodiment 2 is that no dispersant is added, 1.2 g of PVDF
is used, and a larger amount 14 of solvent is used during the preparation of the NCM ternary positive plate.
[0064] A method for preparing a ternary positive plate in Comparative example 2 16 includes: fully dissolving 1,2 g of binder PVDF in 40 g of NMP; adding 10 g of carbon nanotube 17 dispersion (solid content: 5 wt%) and 1.3 g of carbon black as a conductive agent, and performing 18 stirring for 20 min; adding 97 g of positive active material NCM811 (LiNio8C0o1M no 102) and 19 performing stirring for 3 h to obtain a positive slurry; and coating the positive slurry on aluminum foil and performing drying at 130 C for 30 min to form a positive material layer, thereby 21 completing the production of an NCM ternary positive plate.
CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 [0065] In order to support the beneficial effects of the present disclosure, the tested 2 viscosity and solid content of the positive slurry in each embodiment and comparative example, 3 content of the positive active material in the positive material layer, and peeling force of the 4 positive plate are summarized in the following Table 1.
[0066] Table 1 Summary of results of embodiments and comparative examples Viscosity of Solid content of Content of positive active Peeling force of positive slurry positive slurry material in positive positive plate (mPa.$) (%) material layer (%) (N/mm) Embodiment 1 3430 63.0 97.0 Embodiment 2 3560 63.0 97.0 Embodiment 3 3280 63.0 97.0 Embodiment 4 3300 63.0 97.0 Comparative 3390 59.2 97.0 example 1 Embodiment 5 2560 71.7 97.0 Embodiment 6 2470 71.7 97.0 Embodiment 7 2600 71.7 97.0 Comparative 2710 66.9 97.0 example 2 7 [0067] The viscosities of the positive slurries in the above Table 1 are measured by using 8 a rheometer with a reference model of Anton Paar MCR 302. The flexibilities of the positive plates 9 are obtained through visual observation after folding the positive plates in half. The peeling force of the positive plate is tested by using a pressure sensitive binder tape peeling test, with a reference 11 standard GB/T 2792-1998.
CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 [0068]
It may be learned from Table 1 that the viscosities of the positive slurries in Embodiments 1-4 approximate that in Comparative example 1, and the viscosities of the positive slurries in Embodiments 5-7 approximate that in Comparative example 2, both of which satisfy corresponding plate preparation requirements. Through comparison between Embodiments 1-4 and Comparative example 1 and between Embodiments 5-7 and Comparative example 2, it may be learned that the positive slurry including the dispersant provided in the embodiments of the present disclosure has a higher solid content and a shorter time is spent in producing a positive slurry with a desirable dispersion effect in a case that the content of the positive active material in the positive material layer remains unchanged. Moreover, only a small amount of binder PVDF is used, which indicates that the dispersant provided in the present disclosure may partially replace PVDF to provide a bonding function. In addition, the peeling force of the positive plate in the embodiments of the present disclosure is greater than the peeling force of the positive plate in the 13 corresponding comparative example.
14 [0069]
In addition, it may be learned through the comparison between Embodiment 1 and Embodiment 4 that when mass ratios of all components in the monomer raw material are the same, the peeling force of the positive plate using the dispersant prepared using acrylonitrile is 17 slightly greater than that of the positive plate using the dispersant prepared using acrylate.
[0070] The foregoing embodiments show only several implementations of the present disclosure and are described in detail, which, however, are not to be construed as a limitation to the patent scope of the present disclosure. It should be noted that a person of ordinary skill in the art may make several transformations and improvements can be made without departing from the CPST Doc 497037.1 CA Application CPST Ref: 40826/00030 1 idea of the present disclosure. The transformations and improvements belong to the protection 2 scope of the present disclosure. Therefore, the protection scope of the patent of the present 3 disclosure shall be subject to the appended claims.
CPST Doc: 497037.1
Claims (11)
the acrylate monomer comprises one or more of alkyl acrylate, alkyl methacrylate, hydroxyalkyl acrylate, and hydroxyalkyl methacrylate; and the conjugated diene monomer comprises one or more of 1,3-butadiene, isoprene, 2,3-dimethy1-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-decadiene, and 2-methy1-1,5-heptadiene.
performing a polymerization reaction on a monomer raw material comprising a solvophilic monomer, a conjugated diene monomer, and a high-adhesion monomer to obtain the dispersant for a lithium ion battery, wherein the solvophilic monomer comprises one or both of N-vinylpyrrolidone and an actylamide monomer; and the high-adhesion monomer comprises one or both of an unsaturated nitrile monomer and an acrylate monomer.
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| PCT/CN2021/133138 WO2022111580A1 (en) | 2020-11-28 | 2021-11-25 | Dispersant for lithium ion battery, preparation method therefor, positive electrode slurry and lithium ion battery |
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| KR102954236B1 (en) * | 2022-09-27 | 2026-04-20 | 컨템포러리 엠퍼렉스 테크놀로지 (홍콩) 리미티드 | Binder and separator containing the same |
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| WO2022111580A1 (en) | 2022-06-02 |
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| CN114573751A (en) | 2022-06-03 |
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